Carbamylanthraquinone compounds and materials dyed therewith



United States Patent ice 2,937,190 CARBAMYLANTHRAQUINONE COMPOUNDS AND MATERIALS DYED THEREWITH James M. Straley and RalphR GileS, Kingsport,-tTenn., .assignors to Eastman Kodak, Company, Rochester, N.Y., a corporation of New Jersey 5 v No Drawin Application March 10,- 1958 Serial No. 720,072

6 Claims. (c1. zoo -347.4

This invention relates to new anthraquinone compounds and their application to the art of dyeing or coloring.

The dyeing ofpolyester textile materials, such as polyethylene terephthalate, has presented difiiculties. While it is known that the familiar disperse dyes, that is waterinsoluble dyes, employed for the coloration 'of cellulose acetate frequently possess afiinity for polyester textile materials such as polyethylene terephthalate, by far the majority of the known disperse dyes for cellulose acetate exhibit poor fastness to light when applied to polyester textile materials. The new water-insoluble anthraquinone compounds of our invention possess good affinity for polyester textile materials and give red dyeings thereon having good fastness properties, including good fastnes's to light; Additionally, they have good afiinity for 'cellulose acetate, for example, and yield dyeings of high quality thereon.

Polyester fabrics are usually heat set, after dyeing, at temperatures which often reach 400 F. If the dye is not fast to sublimationit will be removed in part, at least, from the goods during" this operation, some'dyes, otherwise suitable for dyeing polyester fabrics, are unsuitable because they are 1101 fast to Sl'lblima'tldn'. 116W anthlaquinoneeompoundsot our invention yield dyeings on the textile materials indicated herein which have excellent fastness to sublimation.

Similarly, dyeings desirably should be fast to solvent rubbing. When-a dry cleaner receives a garment heimay wish to remove the heavier stains by rubbing the garment with a solvent prior" to putting-it with other garments. If the dyeing is not resistant to this treatmentthe spot of spots rubbed with solvent will become lighter in shade. The anthraqu'inone compounds of our invention yield dyeings on the textile material indicated herein which have satisfactory resistance to SIGIVl'it rubbing. V p t It is'an ohect of inventio to provide newianthra quinone compounds. Another object is to provide a satisfactory process for the preparation of our newanthraquinone compounds. A further object is to provide dyed 3 ,190 Patented May 17, 1960 wherein- X represents amethyl group, an ethyl group, a fi-methoxyethyl group or a fi-ethoxyethyl group and Y represents a p alkoxyethyl group, a fi alkoxy-fi ethoxy ethyl group or a tetrahydrofurfuryl' group and wherein alkoxy represents an alkoxy group having 1- to 4- carbon atomsare valuable'dyes'for coloring polyester and cellulose alkyl carboxylic acid ester having-2 to'4 carbon atoms in the acid groups thereof textile materials. These dye compounds when applied to the afioresaid textile ma terials have good afiinity therefor and givered dyeingsof highquality. In general the dyeings obtained have excellent fastness, for example, to light, gas',washing and sublimation.

By cellulose alkyl carboxylic acid esters having two to four carbonatoms in the acid groups, thereof, we mean to include, for example, both hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, cellulose butyrat'e, celluloseacetate-propionate and cellulose acetate-butyrate.

The polyester textile materials that can be dyed with the .new anthraquinone compounds of our invention inelude polyethylene terephthalate textile materials obtained for example as described in US. Patent 2,465,319 patented March 22, 1949, or other polyester textile mate rials formed from analogous fiber-forming linear polyesters, such as polyesters derived from p-bis-(sulfonyhdiben'zoic acid and various aliphatic acids and glyools as polyester textile materials which have good fastness properties. Another object is to provide cellulose alkyl carboxylic acid. ester textile materials which have good fastn'ess properties. A particular object is to pr'ovide dyed polyethylene ter'ephthalat'e textile materials which have good fastnc'ss properties. A further particular ob ject. is to provide dyed. cellulose acetate textile materials which have good fastness properties. a

, We have discovered that the anthraquino'ne compounds having the formula:

wherein X represents a haloformic acid ester having the formula:

Z-CO-Y wherein Z represents a chlorine atom or a bromine atom and Y represents a ,B-alkoxyethyl group, a B-alkoxy-flethoxyethyl group or a tetrahydrofurfuryl group and wherein alkoxy represents an alkoxy group having to 4 carbon atoms. We prefer to'use chloroformic acid esters because these esters'are'readil'y prepared from simple starting materials; namely, phos'gene and the requisite alcohol. I

. We prefer to carry out the condensation reaction between the l,4-diaminoanthraquino'ne' and the haloformic acid ester compound in a neutraLorganic solvent for the" reactants: employed Which is inert under therea'ction eondition's employed.- While solvents" other than those'specifically' disclosed herein can be used we prefer to use, for example, ethers' of ethylene glycol such'as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, for example, ethers of diethylene glycol such as the monoethyl ether of diethylene glycol and the nionoe'thyl ether of diethylene glycol, for example, 'nitrobenzene; dichlorobenzene and trichlorobenzene because suitable re action temperatures can be obtained and the solubility methylgroup, an ethyl group, a fi-methoxyethyl group or a B-ethoxyethyl group with a characteristics of the starting materials and the reaction products are well suited to these solvents. Other suitable solvents are. hydrocarbons such as Solvesso 100,-predominately aromatic, boiling at about 160-190 C. As a practical matter we prefer to use temperatures in excess of 100 C. Temperatures of about 110 C. to about- 145 C. appear to be very practical. Temperatures lower than 100 C. can be used but are not practical because of the increased reaction time required. Similarly, temperatures higher than 145 C. can be employed if desired.

The use of the solvents indicated hereinbefore permits the reaction to be carried out readily at a suitable temperature. The boiling points of the solvents named are such that by maintaining the reaction mixture under reflux a satisfactory reaction temperature results. 1,4 diamino 2 methoxyanthraquinone, 1,4 diamino 2 ethoxyanthraquinone, 1,4 diamino 2 fimethoxyethoxyanthraquinone and 1,4-diamino-2-p-ethoxyethoxyanthraquinone are used in the preparation of the new anthraquinone compounds of our invention when prepared in accordance with the process described herein. fl-methoxyethyl chloroformate, fl-ethoxyethyl chloroformate, p-n-propoxyethyl chloroformate, -nbutoxyethyl chloroformate, p methoxy B ethoxyethyl chloroformate, fl-ethoxy-B-ethoxyethyl chloroformate, fl-n-propoxy-B-ethoxyethyl chloroformate, B-n-butoxy-B- ethoxyethyl chloroformate and tetrahydrofurfuryl chloroformate are illustrative of the haloformic acid ester compounds used in the preparation of the anthraquinone compounds of our invention.

The following examples illustrate the anthraquinone compounds and the process of'our invention.

Example 1 and dyes Dacron and cellulose acetate textile materials, for example, bright red shades having excellent fastness to light.

Example 2 v I 1 gram of l,4-diamine-2-ethoxyanthraquinone, 1 gram of tetrahydrofurfuryl chloroformate and 110 cc. of ethylene glycol monoethyl ether were heated togethen with stirring, at 12'5130 C. until evolution of HCl ceased..

The reaction mixture was then cooled to 0 C. and kept at this temperature for 2 hours. The reaction product (I amino- '2 ethoxy 4 tetrahydrofurfuryloxycarbamylanthraquinone) which precipitated-was recovered by filtration, washed well with cold methanol and dried. It dyes Dacron and cellulose acetate textile materials, for example; bright red shades having excellent fastness to light. The yield was 1.2 gram.

' Example 3 7 l0 grams-0f l,4-diamino-2-methoxyanthratpiinone,

grams of tetrahydrofurfuryl chloroformate and 100cc: of ethylene glycol monomethyl ether were rel-1 3am) gether with stirring until evolution of HCl ceased. The reaction mixture was diluted with methanol to incipient crystallization and then cooled to 0 C. The reaction product (1 amino 2 methoxy 4 tetrahydrofurfuryloxycarbamylanthraquinone) which precipitated was recovered by filtration, washed well with cold methanol and dried. It dyes cellulose acetate and Dacron textile materials for example, bright red shades having excellent fastness to light.

- Example 4 10 grams of 1,4-diamino-2-methoxyanthraquinone, 20 grams of fl-n-butoxy-fl-ethoxyethyl chloroformate and 100 cc. of ethylene glycol monomethyl ether were refluxed together with stirring until evolution, of HCl ceased. The reaction mixture was diluted with methanol to incipient crystallization and then cooled to 0 C. The reaction product ('1 amino 2 methoxy 4 p nbutoxy ,8 ethoxyethoxycarbamylanthraquinone) which precipitated was recovered by filtration, washed well with cold methanol and dried. It dyes cellulose acetate and Dacron textile materials, for example, bright red shades having excellent fastness to light.

Example 5 1.34 grams of I,4-diamino-Z-methoxyanthraquinone, 1.5 grams of fi-methoxyethyl chloroformate and 10 cc. of ethylene glycol monomethyl ether were refluxed together with stirring until no further color change was observed. The reaction mixture was then cooled to 0 C. and the reaction product (1-amino-2-methoxy-4- fl methoxyethoxycarbamylanthraquinone) which precipi tated was. "recovered by filtration, washed well with methanol and dried. It dyes Dacron and cellulose acetate textile materials, for example, bright red shades having excellent fastness to light. The yield was 1.3 grams.

Example 6 By the use of 2 grams of fi-ethoxyet'hyl chloroformate in place of fi-methoxyethyl chloroformate in Example 5, 1 amino 2. methoxy 4 p -,n propoxyethoxyanthraquinone was obtained. It dyes Dacron and cellulose acetate textile materials, for example, bright red shades having excellent fastness to' light.

Example 7 g Example8 By the use of 2.5 grams of fl-ethoxy-B-ethoxyethyl chloroformate in place of B-methoxyethyl chloroformate. in Example 5, 1.6 grams of l-amino-2-.n1etl1oxy-443-vv e'thoxy-p-ethoxyethoxycarbamylanthraquinone was obtained. it dyes Dacron and cellulose acetate textile materials, for example, bright red shades having excellent fastness to light. 7

Following the procedures 1 amino 2 methoxy 4 9 n propoxyethexycarbamylanthraquinone, 1 amino 2 methoxy 4 8- n 'bntoxyethoxycarbamylanthraquinone, 1 amino 2- ethoxy 4 B metboxyethoxycarbamylanthraquinone, 1 amino 2 ethoxy 4 fl ethoxyethoxycarbamylanthraquinone, 1 amino- 2"-*ethoxy="'-' 4 fi methoxy- 5 ethoxyethoxycarbamylanthraquinone, l amino 2- ,3 methoxyethoxy 4 B ethoxyethoxycarbamylanthradescribed hereinbeforespam) whom, 1 amino 2 e methoxyethoxy' 4 tetra.- hydrofurfuryloxycarbamylanthraquinone; I amino 2- ,8 ethoxyethoxy 4 B methoxyetlioiycarbamiylanthraquinone; .1, amino 2. p-l ethoxyethoiiy 4 p ethoxye'thoxyca'rbamylanthraquinone and Famino-Z-p I ethoxy 4:- a ethoxy' d ethoxyethoxycarbamylanthraquinone, for example, arereadily'prepared. All these compounds yield red dyeings on the textile materials disclosed herein which have fastness properties of the character set forth hereinbefore. Many of the intermediates used in the preparation 0 the new anthraquinone dye compounds of the invention are old. However, certain of the intermediates appear i to be new and, accordingly, examples illustrating the preparation of the intermediate compounds are given hereinafter, even though the manner in which they are prepared is believed to be clear from the prior art.

Example 9.Preparati0n of 1,4-diamino-2-fi-methoxyethoxyanthraquinone 5 grams of l-amino-4-p-toluenesulfonamidoanthraquinone-Z-sulfonic acid were added portionwise, with stirring, at 80 C. over a period of about 1 hour to a melt prepared from grams of KOH in 30 cc. of methyl Cellosolve and the reaction mixture resulting was stirred 2 hours longer at 8085 -C. The reaction mixture was then cooled to 40 C. and run into 500 cc. of cold water. The product which precipitated was recovered by filtration, washed with hot water and then dried.

The product obtained as described above was dissolved by stirring in 50 grams of 96% H 80 and after complete solution held at 45'-'50 C. for 1% hours. The

Example 10.Preparatiort of 1,4-diamin0-2-{3-eth0xy ethoxyanthraquinone Example 9 is repeated except that 30 cc. of ethyl Cellosolve are used in place of methyl Cellosolve.

Example 11.-Preptifati0n of fi-methoxyethyl chloroformate Into a 3-ncck flask fitted with a stirrer, gas-inlet tube and Dry Ice trap, cooled in an ice-HCl bath, phosgene was run from a tank until 76 cc. of phosgene had collected in the flask. The stirrer was started and 76 cc. of ethylene glycol monomethyl ether were added dropwise. After complete addition of the ethylene glycol monomethyl ether, the Dry Ice trap was removed and the excess phosgene was distilled off by allowing the temperature to rise to room temperature. The residue in the flask was washed with ice water, dried over CaCl and distilled under vacuum. The fraction boiling at 98-99 C./ 118 mm. was collected and consisted essentially of fl-methoxyethyl chloroformate. A yield of 98.4 grams was obtained.

Example 12.Preparation of fl-ethoxyethyl chloroformate Example 11 was repeated except that 74 grams of ethylene glycol monoethyl ether were used in place of ethylene glycol monomethyl ether. 71 grams of fi-ethoxyethyl chloroformate boiling at 103 C./ 100 mm. were obtained.

Example 13.-Prepara t;ion of p-n-butoxy-B-ethoxyethyl chloroformate butoxy-fi'ethoxyethyl chloroforma'te ant-42mm. were obtained.

Example 14.--*Preparaiion, of ttrahydrbfuffilr'yl chloroformate Example fl was repeated except that 10; grams of tetrahydrofurfuryl alcohol were used'in arse-ear ethylene glycol monomethyl ether and 108 cc. of phosgene were used in place of 76 cc. of phosgene. 90.3 grams of tetra hydro'furfuryl chloroformate boiling at 60-""6'4 'C./1.0- 1.2 mm. were obtained.

The new anthraquinone compounds of our invention can be used to color the polyester and the cellulose alkyl "carboxylic acid ester textile materials mentioned hereinbefore by methods well known to those skilled in the art to which this invention is directed. They'may be dibe conducted at temperatures of about 70-90 C., but 1 any suitable temperature can be used. Thus, the textile materials such as cellulose acetate, for example, to be dyed or colored isordinarily added to the dye bath at a temperature lower than that at which the'main portion of the dyeing is to be eilecte'd, a temperature approximating '45 C.55 C for example, following which the temperature is raised to that selected for carrying out the dyeing operation. a

While the temperatures given in the dyeing procedure just 'set forth apply primarily to cellulose alkyl'carbox'ylic acid ester textile materials, with the modifications indi cated hereinafter, this dyeing procedure also applies to the dyeing of polyester textile materials. jAs understood by those skilled in the dyeing art somewhat higher temperatures than those set forth in the preceding paragraph are'ordinarily employed, when polyester textile materials, such as Dacron, are being dyed. Theselatter materials are fordinan'ly dyed at the boil and usually an assistant, conimonly known as a carrier is employed. The carriers have various active ingredients, sucl ras chlorinated ben'zenes and o phenylphenol, for example, in emulsion. Dacronyx is the tradename of an illustrative suitable carrier."

As is understood by those skilled in the dyeing art, the intensity of dyeing can be varied by varying the proportion of dye to material undergoing coloration. The amount of dye used can be, for example}: to 3% (by weight) of that of the textile material, although lesser or greater amounts of dye can be .iised.

We claim: H l. The anthraquinone compounds having-the formula: 7

c) r's-o-o-Jr N II butoxy p ethboiling? at m 3. 1 amino 2 methoiy 4 tetrahydrofurfuryloxycarbamylan thraquinone 4. 1 amino 2 ethoxy 4; tetrahydrofurfuryloxycarbamylanthr-aquinone.

5. 1 amino --'2 5 methoxyethoxy 4 p methoxyethoxycarbamylanthraquinolie.

6. 1 amino 2 methoxy 4 fi methoxyethoxycarbamylantbraquinone;

Refer-capes Cited infhe file of this patcnt UNITEDSTATESPAIENTS i Lindenstruth June 12,1956

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,937,190 May '17, 1960 James M. Straley et a1.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6, lines 57 to 65, claim 1, the formula should appear as shown below instead of as in the patent:

(f NH! NC-O--Y H 3 Signed and sealed this 29th day of November 1960.

[SEAL] v Attest:

KARL H. AXLINE, Attestz'ng Ofiicer.

ROBERT C. WATSON, Commissioner of Patents. 

1. THE ANTHRAQUINONE COMPOUNDS HAVING THE FORMULA: 